Phytotoxic use of n 1 cycloalken 1 yl ureas and thioureas

ABSTRACT

PHYTOTOXIC USE OF N-(1-CYCLOALKEN-1-YL)AUREAS AND THIOUREAS AND THEIR COMPOSITION.

United States Patent US. Cl. 71-120 15 Claims ABSTRACT OF THE DISCLOSURE Phytotoxic use of N-(1-cycloalken-1-yl)ureas and thioureas and their composition.

This application is a ,continuation-in-part of US. application'Ser. No. 781,588, filed Dec. 5, 1968, now abandoned, which is a continuation-in-part of US. Ser. No. 737,271, filed Apr. 11, 1968 and now abandoned, which in turn is a division of U .8. Ser. No. 523,856, filed Feb. 1, 1966, now abandoned.

The novel N-(1-cycloalken-1-yl)ureas and thioureas of this invention are represented by the formula wherein R is alkyl having a maximum of three carbon atoms, a is one of the integers zero to two; n is one of the integers three to six, R is selected from the group consisting of alkyl having a maximum of twelve carbon atoms, alkenyl having at least three and a maximum of eight carbon atoms, provided that the ethylenic linkage is not on the carbon attached to the nitrogen; alkoxy-alkyl having at least two and a maximum of eight carbon atoms; and benzyl; X is selected from the group consisting of oxygen and surfur; A is selected from the group consisting of (i) Naphthyl, substituted naphthyl said substitution having a maximum of four substituents and being selected from the group consisting of alkyl having a maximum of eight carbon atoms, halogen, mono, diand trihalogenated methyl and nitro, bicycloalkyl and bicycloalkene each having at least seven and a maximum of twelve carbon atoms, substituted bicycloalkyl having a maximum of three substituents and being selected from the group consisting of alkyl having a maximum of eight carbon atoms, halogen, mono, diand trihalogenated methyl and nitro;

(ii) alkyl having a maximum of 12 carbon atoms, and

alkenyl having a maximum of 12 carbon atoms;

(iii) wherein R and R are independently selected from the group consisting of alkyl having a maximum of four carbon atoms, halogen, alkoxy having a maximum of four carbon atoms, nitro, cyano, mono, di-, and trihalogenated methyl group, phenyl, ph'enoxy, benzyl, substituted phenyl, said substituted phenyl having a maximum of three substituents and said substituents being selected from the group consisting of halogen, nitro, alkyl having a maximum of four carbon atoms and alkoxy having a maximum of four carbon atoms, and b and c are each one of the integers zero to three, inclusive, provided that the total of b+c is a maximum of three.

In the above formula group A includes but is not limited to naphthyl, hydrindane, decalin, bicyclo [523:0] decane, bicyclo [4:2z0] octane, bicyclo [3:3z0] hexane, bicyclo [2,2,2] octane, bicyclo [2,2,1] hept-2-ene, bicyclo [2,2,1] heptane, Z-methylbicyclo [2,2,1] heptane, 2- chloronorcamphane, l-nitronorcamphane, S-methylnorborene, norbornadiene, bicyclo [2,1,2,1] decane, 2-methylnaphthyl, 2-ethylnaphthyl-2-n-octylnaphthyl, 2,3,6-trimethylnaphthyl, 2-chloronaphthyl, and 2-iodonaphthyl.

A preferred embodiment of the compounds of this invention are the compounds in which the group A is defined by the group:

wherein R R b and c are as previously defined.

In the above general formula R includes but is not limited to methyl, ethyl, n-propyl and iso-propyl; R includes but is not limited to methyl, ethyl, propyl, isopropyl, butyl and its isomers, pentyl and its isomers, octyl and its isomers and dodecyl and its isomers, allyl, n-

- buten-l-yl, n-buten-r2-yl, Z-methylpropen-l-yl, n-penten-lyl, 3-methylbuten-l-yl, n-hexen-Z-yl, n-hepten-l-yl, 3,3-dimethylpenten-l-yl, l-methylhexen-l-yl, n-octen-l-yl and the various homologues and isomeric forms of alkenyl having 3 to 8 carbon atoms; methoxymethyl, methoxyethyl, methoxypropyl, methoxybutyl, methoxyheptyl, ethoxyethyl, propoxypropyl, ethoxypropyl, ethoxybutyl, butoxybutyl and the like.

The group (0112),; O=NR ANCX H C R x Ralf Cmaal wherein R R A, X, a and n are as previously defined.

Temperature of reaction is critical but only in regard to the upper limit employed for specific isothiocyanate reactions, according to the above equation. When the isothiocyanate reactant is a substituted aryl selected from the group consisting of haloaryl, cyanoaryl or nitroaryl isothiocyanate, the reaction temperature is critical and must be maintained below about 35 C. If this process is carried out for a substantial period, with these specific isothiocyanate reactants, at temperatures above about 35 C. thermal rearrangement of the N-(l-cycloalken-l-yl)-N- (substituted aryl)thioureas proceeds according to the following representative example:

s RLN= ClArNCS IU-If-(iJ-NHArCI NHR wherein R is as previously defined and Ar is aryl. In carrying out the processes of this invention, other than that heretofor specified for selective thioisocyanates, the reaction temperature is not critical and temperatures from about C. to about 100 C. are usually employed with the temperatures from about C. to about 60 C. being preferred.

The process of this invention is usually carried out with substantially equimolar amounts of reactants but an excess of either reactant can be used if desired. The processes are advantageously carried out in the presence of an inert organic medium. Inert organic media which can be used in the practice of this invention include, but is not limited to, hydrocarbons such as benzene, toluene, xylene, cyclohexane, methylcyclohexane, n-hexane, n-heptane and the like, ethers such as tetrahydrofuran, n-butyl ether, 1,4- dioxane, isobutyl ether, diethyl ether and the like, organic halides such as carbon tetrachloride, n-butyl chloride, methylene chloride, ethylene dichloride, tetrachloroethylene and the like, and esters, such as ethyl acetate, propyl acetate and the like, and solvents such as dimethyl sulfoxide, N,N-dimethylformamide and the like.

The separation of the resulting reaction product from the reaction mixture is readily accomplished. The solvent can be removed from the reaction mixture by conventional means, for example, by stripping or distillation, preferably low temperature vacuum distillation. The product, if desired, can be purified by any of the conventional means well known in the art, e.g. extraction, fractional distillation using a carrier gas, film distillation and recrystallization or any suitable combination of these.

In accordance with this invention it has been found that the growth of germinant seeds, emerging seedlings, and established vegetation can be controlled and modified by exposing the seeds, emerging seedlings, or the roots or above-ground portions or established vegetation to the action of an effective amount of one or more of the N-(1-cycloalken-1-yl)ureas and thioureas represented by the formula R X (CH. C l l LIJ wherein R R A, X, n and a are as defined above, and in particular compounds of the formula wherein R R R R X, n, a, b and c are as previously defined. These compounds are effective as general phytotoxicants including post-emergent phytotoxicants and preemergent phytotoxicants. Furthermore, these compounds are characterized by a broad spectrum of herbicidal or phytotoxic activity, i.e. they modify the growth of a wide variety of plant systems including both broadleaf and grass plants. For the sake of brevity and simplicity, the term active ingredient will be used hereinafter in this specification to describe the novel phytotoxicants of the above formula.

The phytotoxic or herbicidal compositions of this invention contain at least one active ingredient and a material referred to in the art as a phytotoxic adjuvant in liquid or solid form. The phytotoxic compositions are prepared by admixing the active ingredient with an adjuvant including diluents, extenders, carriers and conditioning agents to provide compositions in the form of finelydivided particulate solids, granules, pellets, solutions and aqueous dispersions or emulsions. Thus the active ingredient can be used with an adjuvant such as a finely-divided particulate solid, a solvent liquid of organic origin, water, a wetting agent, dispersing agent, an emulsifying agent or any suitable combination of these.

Typical finely-divided solid carriers and extenders which can be used in the phytotoxic compositions of this invention include for example, the tales, clays, pumice, silica, diatomaceous earth, quartz, Fullers earth, salt, sulfur, powdered cork, powdered wood, walnut flour, chalk, tobacco dust, volcanic ash, and the like. Typical liquid diluents include for example, kerosene, Stoddard solvent, hexane, benzene, toluene, acetone, ethylene dichloride, xylene, alcohols, Diesel oil, glycols and the like.

The phytotoxic compositions of this invention, particularly liquids and wettable particles, usually contain as a conditioning agent one or more surface-active agents in amounts sufficient to render a given composition readily dispersible in water or in oil. By the term surfaceactive agent it is understood that wetting-agents, dispersing agents, suspending agents and emulsifying agents are included therein.

The term phytotoxic composition as used herein and in the appended claims is intended to mean not only compositions in a suitable form for application but also concentrated compositions which require dilution or extension with a suitable quantity of liquid or solid adjuvant prior to application.

The following examples will illustrate the invention. In these examples, as well as in the specification and appended claims, parts and percent are by weight unless otherwise indicated.

EXAMPLE 1 This example describes the preparation of l-(l-cyclohexen- 1-yl)-1-(methyl)-3-(o-nitrophenyl) urea.

To a solution of 8.2 parts of o-nitrophenyl isocyanate in carbon tetrachloride maintained at room temperature is added about 5.5 parts of N-cyclohexylidene N-methyl amine. An exothermic reaction occurs and the reaction mixture warms to about 30 C. The reaction mixture is cooled to about room temperature (25 C.) and stirred for about 30 minutes. The carbon tetrachloride is stripped 01f at reduced pressure to recover a reddish-orange solid product which after being re-crystallized twice from ethyl alcohol has a melting point of 120.5-122 C. The assigned structure is confirmed by nuclear magnetic resonance (NMR) spectrum analysis.

Calcd for C H N O' (percent): C, 61.0; H, 6.19; N, 15.3. Found (percent): C, 60.87; H, 6.24; N, 15.61.

EXAMPLE 2 This example describes the preparttion of l i (oHmom -d-N-Q-m 1 (1 cyclohexen 1 yl) 1 (isopropyl) 3 (3,4- dichlorophenyl)urea.

To a solution of 18.8 parts of 3,4-dichlorophenyl isocyanate in benzene maintained at room temperature is added about 13.9 parts of N-cyclohexylidene-N-isopropylamine. An exothermic reaction occurs and the reaction mixture warms to about 30 C. The reaction mixture is cooled to room temperature, stirred for about three hours and the benzene stripped off at reduced pressure to recover the oily product. The assigned structure is confirmed by NMR spectrum analysis.

Calcd for C H N 'OCl (percent): N, 8.56; Cl, 21.7. Found (percent): N, 7.92; CI. 19.4.

EXAMPLE 3 This example describes the preparation of s i omwHmomN- -NQm 1 (1 cyclohexen 1 yl) 1 (n butyl) 3 (3,4 dichlorophenyl)-2-thiourea.

To a solution of 20.4 parts of 3,4-dichlorophenyl isothiocyanate in carbon tetrachloride maintained at about C. is added about 15.3 parts of N-cyclohexylidene-N- (n-butyl) amine. An exothermic reaction occurs and the reaction mixture warms to about 30 C. The reaction mixture is cooled to about 15 C. and stirred for about one hour. The carbon tetrachloride is stripped oif at reduced pressure to recover an oily product which is crystallized from hexane. The solid product amounts to 33 parts and has a melting point of 9596 C .The assigned structure is confirmed by NMR spectrum analysis.

Calcd for C H NSCl (percent): C, 57.2; H, 6.26; N, 7.85; S, 8.96. Found (percent): C, 56.58; H, 6.12; N, 7.91; S, 9.21.

EXAMPLE 4 This example describes the preparation of i i omN-c- Q01 1 (1 cyclohexen 1 yl) 1 methyl 3 (p chlorophenyl)-2-thiourea.

To a solution of 11.1 parts of p-chlorophenyl isothiocyanate in carbon tetrachloride maintained at about C. is added about 16.9 parts of N-cyclohexylidene-N- methyl amine. An exothermic reaction occurs and the reaction mixture warms to about 30 C. The reaction mixture is cooled to about 20 C. and stirred for about four hours. The carbon tetrachloride is stripped off at reduced pressure to recover a solid product which after being recrystallized from hexane has a melting point of 106107 C. The assigned structure is confirmed by NMR spectrum analysis.

Cald for C H N SCI (percent): C, 60.0; H, 6.07; N, 10.0; C1, 12.7; S, 1'1.4. Found (percent): C, 59.28; H, 6.08; N, 10.10; Cl, 12.97; S, 11.79.

EXAMPLE 5 This example describes the preparation of s H ll 1 CH3N- --N-O2H5 1 (1 cyclohexen 1 yl) 1 (methyl) 3 (ethyl 2- thiourea.

To a solution of 8.7 parts of ethyl isothiocyanate in toluene maintained at about 15 C. is added about 11.1 parts of N-cyclohexylidene N-methyl amine. An exothermic reaction occurs, and the reaction mixture warms to about 30 C. The reaction mixture is cooled to about 20 C. and stirred for about three hours. The solvent is stripped ofi at reduced pressure and the residue is fractionally distilled to recover the product fraction boiling in the range of 45-55 C., at a pressure of 10 mm. of mercury. The product amounts to about 17 parts and has a melting point of 4344 C. The assigned structure is confirmed by NMR spectrum analysis.

Calcd for C H N S (percent): N, 14.15; S, 16.15. Found (percent): N, 14.15; S, 15.80.

EXAMPLE 6 This example describes the preparation of 1 (1 cyclohexen 1 yl) 1 (methyl) 3 (3,4 dichlorophenyl) urea.

To a solution of 18.8 parts of 3,4-dichlorophenyl isocyanate in toluene maintained at about 15 C. is added about 11.1 parts of N-cyclohexylidene N-methyl amine. An exothermic reaction occurs, and the reaction mixture warms to about 35 C. The reaction mixture is cooled to room temperature and stirred for about 30 minutes. The toluene is stripped oif at reduced pressure to recover 22 parts of oily product. The assigned structure is confirmed by NMR spectrum analysis.

Calcd for C I-I N OCl C, 56.2; N, 9.36. Found (percent): C, 55.57; N, 9.36.

EXAMPLE 7 S r CHgN-liL-N-(CHMCHa This example describes the preparation of 1 (1 cyclohexen 1 yl) 1 (methyl) 3 (nbutyl)-Z-thiourea.

To a solution of 11.5 parts of n-butylisothiocyanate in toluene maintained at about 15 C. is added about 11.1

parts of N-cyclohexylidene N-methyl amine. An exothermic reaction occurs and the reaction mixture warms to about 30 C. The reaction mixture is cooled to room temperature and stirred for about 24 hours. The solvent is stripped otf at reduced pressure and the residue is fractionated to recover the product oil. The assigned structure is confirmed by NMR spectrum analysis.

Calcd for C H N S (percent): N, 12.4; S, 14.15.

Found (percent): N, 12.28; S, 14.02.

EXAMPLE 8 This example describes the preparation of II CHtIf-C-NCH:

1--( l-cyclohexen-l-yl)-l (methyl)-3-methyl urea.

trum analysis.

Calcd for C H N O (percent): C, 64.3; H, 9.52; N,

16.65. Found (percent): C, 63.14; H, 9.53; N, 16.56.

Following the procedure of the foregoing examples and using the appropriate isocyanate or isothiocyanate and cyclohexylidene amine reactants, the following l-(l-cyclohexen-l-yl) ureas were prepared.

Example 9 l-(l-cyclohexen-l-yl)-1-(ethyl)-3-(butyl) urea.

10- 1-(1-cyclohexen-1-yl)-1-(allyl)-3-(rn-ehl0rophenyl) urea.

11- l-(l-cyclohexen-l-yl)-1-(2-buten-1-yl)-3-(phenyl) urea.

12 1- (l-cyclohexen-l-yl) -1-(sec-butyl) -3-(2,6-dich1orophenyl) urea.

13 1-(1-cyclohexen-1-yl)-1-(methoxyethyl)-3-(2,4,6-trichlorophenyl) urea.

14. l-(l-eyclohexen-l-yl)-1-(methoxypr0pyl)-3-(allyl) urea.

-y urea.

16 l-(l-cyclohexen-l-yl)-1-(methoxyamyl)-3-(2,4-dinitrophenyl) urea.

17. l-(l-cyelohexen-l-yl)-1-(butyl)-3-(rnethy1)-2-thiourea.

18- 1-(1-cyclohexen-1-yl)-1-(hexyl)-3-(allyl)-2-thiourea.

20. l-(l-cyelohexen-l-yl)-1-(penten-1-yl)-3-(phenyl)-2-thlourea.

21 l-(l-cyclohexen-l-yl)-1-(methoxypropyl)-3-(m-nitrophenyl)- 2-thiourea.

22 1-(1-cyclohexen-1-yl)-1-(ethyl)-3-(2,4-dinitrophenyl)-2- thiourea.

23 l-(lbyclohexen-l-yl)-1-(eth0xyethyl)-3-(p-chlorophenyl)- 2-thiourea.

24 l-(l-cyclohexen-l-yl)-l-(methoxyhexyl)-3-(rnethyl)-2- thiourca.

25 l-(bcyclohexen-l-yl)-1-(methyl)-3-(buten-1-yl)-2-thiourea.

27 1-(2-rnethyl-6-isopropyl-l-cyclohexen-l-yl)-1methy1-3-(ofluorophenyl) urea.

28 l-(l-cyclopenten-l-yl)-1-methyl-3-(o-fiuorophenyl) urea.

29 1-(2-methyl6ethyl-l-cyclohexen-l-yl)-lmethyl-3-phenylurea.

30 l-(l-cyelohexen-l-yl)-1-(ethy1)-3-(p-methylphenyl) urea.

31 1-(l-cyclohexen-l-yl)-1-(metl1yl)-3-(2,4-dimethylphenyl) urea.

32 l-(l-cyclohexen-l-yl)-1-(methyl)-3-(2,4,6-trimethylphenyl) urea.

33 1-(2-ethy1-1-eyclopenten-1-yl)-1-propyl-3-(o-fluorophenyl) urea.

34 1-(2-methyl-fi-isopropyl-l-cyclol1epten-1-yl)-1-methyl-3- (o-fluorophenyl) urea.

35 1-(imethyl-l-cyclohexen-1-yl)-l-mcthyl-3-(o-fluorophenyl) t iourea.

36 l-(l-cyclohexen-l-yl)-1-(methyl)-3-(3,4-dirnethylphenyl) urea.

37 l-(l-cyclohexen-l-yl)-1-(methyl)-3-(3,4-dimethylphenyl)- 2-thiourea.

38 l-(il-cyclohexen-l-yl)-1-(methyl)-3-(m-methylphenyD-2- t iourea.

39 1-(2-methyl-l-cyclohexen-1-yl)-1-ethyl-3-(3-chloro-4-methoxyphenyl) urea.

40 1-(2-isopropyl-1-cyclohepten-l-yl)-1-methyl-3-(o-fiuorophenyl) urea.

41 l-(l-cyclohexen-l-yl)-1-methy1-3-(m-trifluoromethylphenyl) urea.

TABLEContlnued Example 42 l-(l-cyclohexen-l-yl)-1-methyl- -(3-chloro-4-methoxypheny urea. l-(l-cyclohexen-l-yl)-1-methyl-3-(o-trlfluoromethylphenyl) urea. 1-(1-cyclohexen-1-yl)-l-methyl-3-phenyl urea.

l-(l-cyclohexen-l-yl)-1-methyl-3-(3-chloro4-methylphenyl) urea. l-(l-cyclohexen-l-yl)-1-methyl-3-(2-biphenyl) urea. l-(l-cyclohexen-l-yl)-1-rnethyl-3-phenoxy-rncthyl urea. l-(l-cyclohexen-l-yl)-1-methy1-3-(4-fiu0rophenyl) urea. l-(l-cyclohexen-l-yl)-1-methyl-3-(4-ethoxyphenyl) urea. l-(lpyclohexen-l-yl)-1-mcthyl-3-(4-methoxypheny1) urea. 1-(l-cyelohexen-l-yl)-1-rnethyl-3-(4-n1ethylphenyl) urea. l-(l-cyclohexen-l-yl)-1-methyl-3-(2,5-dichlorophenyl) urea. 1-(l-cyclohexen-l-yl)-1-methyl-3-n-butyl urea. 1-(l-cyclohexen-l-yl)-1-methyl-3-(2-methylphenyl) urea. l-(l-cyclohexen-l-yl)-1-methyl-3-[4-(4-chlorophenoxyphenyl)] urea. 1-(1-cyclohexen-1-yl)-l-rnethyl-3-(3-methyl phenyl) urea. l-(l-cyclohexen-l-yl)-1-methyl-3-methylene-carboethoxy) urea. 1-(l-cyclohexen-l-yl)-1-methyl-3-(3-chlorophenyl) urea. 1-(l-cyclohcxen-l-yl)-1-rnethyl-3-(2-chlorophenyl) urea. 1-(l-cyclohexen-l-yl)-1-methyl-3-(2-fluorophenyl) urea. l-(l-cyclohexen-l-yl)-1-methyl-3-(4bromophenyl) urea. 20 62 l-(2,G-dimethyl-l-cyclohexen-1-y1)-1-methyl-3-(3,4-dichlorophenyl) urea. 63 1-(2,6-dimethyl-l-cyclohexen-l-yl)-1-methyl-3-(4-chlorophenyl) urea. 64 1-(2,6-dimethyl-1-cycl0hexen-1-yl)-1-methyl-3-phenylurca. 65 1-(2-n-propyl-1-cyclohexen-l-yl)-1-mcthy1-3-(4-chlorophenyl) urea. 1-(2-n'propyl-1-cyclohexen-l-yl)-1-methyl-3-phenylnrea. 1-(6-n-propyl-l-cyclohexen-l-yl)-1-rnethyl-3-phenylurea. 1-(2-methyl-l-cyclohexen-l-yl)-l-mcthyl-3-(3,4-dichloro phenyl) urea. 1-(2-methyl-l-cyclohexen-l-yl)-1-methy1-3-(4chlorophenyl) urea. 1-(6-111ethyl-bcyelohexen-l-yl)-1-methyl-3-(4-chloropheny1) urea. 1-(2-methyl-1-cyclohexen-1-y1)-1-methoxyethyl3-(3,4-diehlorophenyl) urea.

73 1-(fi-methyl-leyclohexen-l-y1)-1-methoxyethyl-3(3,4-dlchlorophenyl) urea. 74 1-(2-methyl-l-cyclohexen-l-yl)-1-mcthoxyisopropy1-3-(3,4- 35 dichlorophenyl) urea.

75 1-(2-ethyl-1-cyc1ohexen-1-y1)-1-ethoxy-ethyl-3-(o-fluorophenyl) urea. 1-(Z-methyl-Lcyclohexen-l-yl)-1-methy1-3-(3,4-d1chlorophenyl) urea. 1-(fi'methyl-l-cyclohexen-l-yl)-1-methy1-3-(3,4-dichlorophenyl) urea. 1-(3,5-dimethy1-1-cyclohexen-1-yl)-1-metl1oxyethy1-3-(3,4-

dichlorophenyl) urea. l-(l-cyclohexen-l-yl)-1-methyl-3-(4-carbomethoxy phenyl) thiourea. l-(l-cyclohexen-l-yl)-1-rnethyl-3-n-buty1 thiourea. l-(l-cyclohexen-l-yl)-1-methy1-3-(2-chlorophenyl) thiourea. l-(l-eyclohexen-l-yl)-1-methyl-3-(4-nitrophenyl) thlourea. l-(1-cyclohexen-1-yl)-1-methyl-3-ethylthiourea.

l-(l-cyclohexen-l-yl)-1-metl1yl3-( t-nitrophenyl) thiourea. l-(l-cyclohcxen-l-yl)-1-dodecyl-3-(3,4-dichlorophcnyl) thicurea. l-(l-cyclohexen-l-yl)-1-methy1-3-(3,4-dichlorophenyl) mmure l-(l-cyclohexen-l-yl)-1-methy1-3-(3,4-dichlorophenyl) urea. 1-(1-cyclohexen4-y1)1-methyl-S-metlrylthiourea. l-(l-eyclohexen-l-yl)-1-methy1-3,3-dimethyl urea.

l-(l-cyclopenten-l-yl)-1-methy1-3-(4-nitrophenyl) urea. 1-(2-rnethyl-l-cyclopenten-l-yl)-1-mcthyl-3-(3,4dichloro phenyl) urea. l-(l-cycloocten-l-yl)-1-ethyl-3-(2-fiuorophenyl) urea.

93 l-(l-cyclononen-l-yl) -1-ethy1-3-(2-fiuorophenyl) urea. 94 1-(l-cyclohexen-l-yl)-1-methyl-3-(4-cl1loron1ethylphenyl) urea. 55 95 1-(1-cyclohexen-1-yl)-1-isopropy1-3-(4-dich1oromethylphenyl) urea. 96 l-(l-cyclohexen-l-yl)-1-ethy1-3-(4-benzylphenyl) urea. 97 1-(l-cyclohexen-l-yl)-1-n1ethy1-3-[4-(4-methylphenoxyphenyl)] urea. 98 1-(1-cyelohexen-1-yl)-l-ethyl-3-(4-methylblpheny1) urea.

10 EXAMPLE 99 (TABLE I) cal scale for the sake of brevity and simplicity in the The pre-emergent phytotoxicity of representative N-( 1- examples cycloalken-l-yl) ureas of this invention was demonstrated Them-emergent Phytotoxic activity index used in the as follows: A good grade of top soil was placed in alumi followmg example was defined as follows: num pans and compacted to a depth of to /2" from I the top of each pan. A predetermined number of seeds Phytotoxlc i Numencal Scale of each of several plant species were placed on top of the 9 phytotoxlcliy. 0 soil in the pans. The phytotoxic compositions were applied Shght Phytotoxlclty to the soil by two methods: Moderate Phytotoxicity (1) Application to the surface of the top soil layer, Severe Phytotoxicity 3 and (2) Admixture with or incorporation in the top soil The pre-emergent phytotoxic activity of some of the lawn N-(l-cycloalken-l-yl) ureas of this invention was re- In the surface application method the seeds were corded in Table I for various application rates of the acered with a :y layer f prepared soil and the pan1eve1e tive ingredients 1n both surface and soil-incorporation ap- Th phytotoxic composition was applied by Spraying the plications. In Table I the 5 lb./acre applications were surface of the top layer of soil, prior to watering the seeds, e y the Surface application method and t e 1 1b./ acre with a solution containing a sufiicient amount of active aPPheeltlOIlS Were made y t e S il incorporation method.

ingredient to obtain the desired rate per acre on the soil Results and further details are given below in Table I.

TABLE L-PRE-EMERGENT PHYIOTOXIC ACTIVITY OF VARIOUS N-(1-CYCLOHEXEN-1-YL) UREAS Lbs./ Morning Wild Brome Rye Rad- Sugar Fox; Crab Pig- Soy- Wild Compound acre glory oats grass grass lsh beets tail grass weed been buckwheat Tomato Sormmcnulmcncnmmmmoxozmcnencnoucncneacncnucucncucn HI-IOHDOWHOHQHOHOOOONONI-OQWOOO HHQHOONMNll- NONOOOQCOMOOOWOOH HMOHOQHI-IHHOHHHOJOHOWHNOHOWHQHH HNOHHONNHOOHOHI-H-IOD-IHQNOHOOOHHHW NHHOHHMNMHQOOhnovowowwoczoocfi mmtoiwvwwwmwi-cioauwvoomcrowiwrco MNONQQHI- NHHHMwNMHHNwMowwwNMwN WOJOOJMOWCDWCADHWNWNNHHOJNNOOJHOJWQIW (0WN03NWCIJWWOOWMMNWNWNNHNOWWWWWWW NHOOOOQOQOQOOOQOOOHQHQHOHb- OOrlotlocumtoP-MwMHcHo- HoHHcMHHoMHO- oco NkOHi-I-ONNOJNHQOHNOHOOOWOMOWMOHW 5' l-N- OO0OOHHOOHOHHOQOOHMOOOWOQHW E COMPOUNDS (1) 1-(l eyelohexen-l-ylg-3-(3,4-dichlorophenyl)-1-methylurea. methylurea and 1-(fi-methyl-l-cyelohexen-l-yl)-3-(4-eh1oropheny1).1. (2) l-(l-eyclohexen-l-yl -3-(3,4-dich1orophenyl)-1-methyl-2thionrea. methylurea. (3) l-(l-cyclohexen-l-yl)-3-(o-nitr0phenyl)-1-methylurea. (15) A mlxture of 1-(2-propyI-1-cyclohexen-1-yl)-8-phenyl-1-methy1urea (4) l-(l-eyclohexen-l-yl)-3-(2-flupr0phenyl)-1-methylu.rea. and 1-(6-propyl-l-cyclohexen-l-yl)-1methyl-3-phenylurea. (5)3-(1-cyc1ohexen-1-yl)-1,1,3-tr1methylurea. (16)A mixture of 1-(2-propyl-1-cyc1ohexen-1-yl)-3-(4-chlorophenyl)-1- (6) l-(l-eyclohexen-l-yl)-1-methyl-3-(ortho-nitrophenyDurea. methylurea and 1-(6-propyl-l-cyclohexen-l-yl)-3-(4-chlorophenyl)-l- (7) 3-(ortho-chlorophenyl)-1-(l-eyclohexen-l-yl)1-methyl-2-thiourea. methylurea. (8) 1-(2-methyl-1-cyclohexen-1-y1)-1-methyl-3-(ortho-fluorophenyl)urea (17) l-(l-cyclohexen-l-yl)-3-(4-bromophenyl)-1-methylurea.

mixture with 1-(fi-methyl-l-eyclohexen-1-yl)-3-(ortho-fluorophenyl)-1- (18) 1-(1-cyclohexen-1-yl)-3-(2-chlorophenyl)-1-methylurea.

methylurea. (19) 1-(l-cyclohexen-l-yl)-8-pheny1-l-methylurea. (9) 1-(3,4-diehlorophenyl)-8-(2-methyl-1-cyclohexen-1-yl)-2-thiou.rea. -eyclohexen-l-y )-3-( 'D Y 17 11rea. (10) 1-(Z-ethyl-l-cyclohexen-l-yl)-3-(3,4-diehlor0phenyl)2-th1ourea. -eycl0hexen-1-y1)-3-(3-ch10rophenyl)-1-methylurea. (11) 1-(3,5-dimethyl-l-cyclohexen-l-yl)-3-(3,4-dichloropl1eny1)-1-(2- (22) 1-(1-eyclohexen-1-yl)-3-n1eta-tolyl-l-methylnrea.

th xy th bma, (23) l-(l-cyclohexen-l-yl)-3-[4-(para-chlorophenoxy)pheny11-1-methyl- (12) A mixture of1-(2-methyl-1-cyclohexen-l-yl)-3-(3,4-d1chlorophenyl)-1- urea.

methylurea and 1-(ti-methyI-Lcyclohexen-l-yl)-3-(3,4-dichlorophenyl)- (2A) 1-(l-cyclohexen-l-yl)-3-(2,5-dich1orophenyl)-1-methylurea.

l-methylurea. (25) I-(LcyclOhexen-I-yI)-3-(para-tolyl)-1-methylurea. (13) A mixture oi1-(2-methyl-1-cyclohexen-1-yl)-3-(3,4-d.ichlorophenyl)-1- (26) l-(para-amsyl)-3-(1-cye1ohexen-1-yl)-3-methylurea.

(2-methoxyethyl)urea and 1-(6-methyl-1-cyclohexen-1-yl)-3-(3,4-di- (27) l-(l-cyclohexen-l-yl)-3-(para-fluoropheny1)-1-methylurea.

chlorophenyl)-1-(2-methoxyethyl)urea. (28) l-(l eyclohexen-l-yl)-3-(alpha,alpha,alpha-trifluorometa-tolyl)-1- (14) A mixture of 1-(Z-methyl-l-eyclohexen-l-yl)-3-(4-chlorophenyl)-1- methylurea.

surface. In the soil incorporation method, the soil re- The data in Table I illustrate the general phytotoxic quired to fill the pans was weighed and admixed with activity as well as the selective phytotoxic activity of some a phytotoxic composition containing a known amount of of the N-(l-cycloalken-l-yl) ureas of this invention. It active ingredient. The seeds were then covered with the l be noted that unusual grass Specificity is Obtained at admixture and leveled. Initial watering was carried out low application rates, for example at 1 lb./acre with by permitting the soil to absorb moisture through the N-(l-cyclohexen-l-yl)-3-(3,4-dichlorophenyl) -1-methy1 apertured bottom of the pans. urea.

The seed containing pans were placed on a Wet sand EXAMPLE 100 (TABLE II) bench and maintained for approximately 14 days under 7 This example demonstrates the posbemergent phyt ordinary conditions of sunlight and watering. The plants toxic activity or representative N (1 cyc1oa1ken 1 y1) Were Observed at the end of eppToXimately 14 y and ureas of this invention. The active ingredients were apthe results recorded. The phytotoxic activity index was lied in spray form to 14day old specimens of the same based on the average percent germination of each seed plant species used in the pre-emergent tests above. The lot. The activity index was converted to a relative numeriphytotoxic sprays were acetone-water solutions contain- Phytotoxic Numerical activity scale No phytotoxicity Slight phytotoxicity 1 Moderate phytotoxicity 2 Severe phytotoxicity 3 Plants dead 4 The identification of the plants used was the same as in the above pre-emergent tests. Results and further details are given below in Table II.

Alligator weed cuttings were planted in a pot and allowed to become established over a three-week period. The active ingredient was applied to either the plant foli' age or the water surrounding and in contact with the plant according to the following procedure:

(a) The plants to be submerged were placed in 1 gallon jugs containing 3 liters of one-day old tap water which had been aerated for 15 minutes. A 3% solution of active ingredient was prepared from 0.3 gm. of active ingredient, 0.2 ml. emulsifier and 10 ml. acetone. One milliliter of the 3% solution was then added to the 3 liters of water in which the plant was submerged thus giving an amount of active ingredient equivalent to 10 p.p.m. The effects were observed and recorded after approximately two weeks;

(b) The active ingredient was prepared in a 1% solution (acetone-water solution). The foliage was sprayed with 1.6 ml. of a solution prepared by diluting 0.84 ml. of the 1% solution to a volume of 1.6 ml. This rate of TABLE II.POST-EMERGENT PHYIOTOXIC ACTIVITY OF VARIOUS N-(l-CYCLOHEXEN-l-YL) UREAS Lbs./ Morning Wild Brome Rye Rad- Sugar Fox- Crab Pig- Soy- Wild Sor- Compound acre glory oats grass grass ish beets tail grass weed bean buckwheat Tomato ghum vh wwzonzowmunwwwwwwwwlow-evane cence:wzocewtowwp COMPOUND EXAMPLE 101 (TABLE III) This example demonstrates the aquacide activity of representative N-( l-cycloalken-l-yDureas of this invention.

(17) A mixture of 1-(2-propyl-l-cyclohexen-I-yl)-3-(4-chlorophenyl)- l-methylurea and 1-(6-propy1-1-cyclohexen-1-yl)-3-(4-ehlorophenyl)- l-methylurea.

(18) 1-(2,fi-dimethyl-l-cyelohexen-l-yl)-3-phenyl-1-methylurea.

(19)1 1-(2,6-dimethyl-1-eyclohexen-1-yl)-3-(3,4-dichlorophenyl) -1-methy urea.

(20) 1-(1-cyclohexeu-1-yD-3-(4-bromophenyl)-1-methylurea.

(21) l-(l-eyelohexen-l-yl)-3-(2-chlorpohenyl)-1-methylurea.

(22) 1-(l-cyelohexen-l-yl)-3-phenyl-1-methylurea.

(23) l-(l-cyclohexen-l-yl)-3-(3-chloro-para-toly1)-1-methylurea.

(24) l-(l-cyelohexen-l-yl)-3-(3-chlorophenyl)-1-methylurea.

(25) 1-(l-eyclohexen-l-yl)-3-meta-tolyl-1-methylurea.

(26)1 l-(l-cyclohexen-l-yl)-3-[4-(parachlorophenoxy) phenylI-l-methy urea.

(27) 1-(1-cyelohexen-1-yl)-3-ortho-tolyl-l-methylurea.

(28) 1-(l-cyclohexen-l-yl)-3-(2,5-dichlorophenyl)-1-methylurea.

(29) l-(l-eyclohexen-l-yl) -3-(para-tolyl) -1-methylurea.

(30) l-para-anisyl)-3-(l-eyclohexen-l-yl)-3-methy1urea.

(31) 1-(1-eyelohexen-1-yD-3-(para-ethoxyphenyl)-1-methylurea.

(32)1-(1-cyelohexen-1-yl (para-fiuorophenyl)-1-methylurea.

(33) l-(l-eyelohexen-l-yD- -methy1-3-[ortho-(alpha,alpha,alpha-trifluoromethyl) phenyl] urea.

(34) l-(l-cyclohexen-l-yl)-3-alpha,alpha,alpha-trifluorometa-tolyl)- l-methylurea.

(35) 1-(l-cyclohexen-1-yl)-3-(3-chloro-para-anisyl)-1-methylurea.

(36) 1-(1-cyclohexen-1-yD-3-ethy1-1-methyl-2-thiourea.

application was equivalent to 8 pounds per acre. The effects were observed and recorded after approximately two weeks;

The results were recorded in Table III.

TABLE III.-AQUACIDE ACTIVITY Compound (a)=1-(1-cyclohexen-1-y1)-1-methyl-3-(3,4-diehloropheny1) urea.

Compound (b) 1 (l-oyclohexen-l-yl)-1-methyl-3 (o -fiuorophenyl) urea.

The aquacide activity used in this example was based on the average percent injury and was defined as follows:

Aquacidal activity Numerical scale No injury Slight injury 1 Moderate injury 2 Severe injury 3 Plants dead 4 EXAMPLE 102 This example also demonstrates the aquacide activity of representative N-(1-cycloalken-l-yl)ureas of this invention.

To a set of 100 by 15 mm. Petri plates which were divided into sections, 4.5 ml. of Eysters nutrient solution were added. To each plate section 12 fronds of healthy giant duckweed (Spirodela polyrhiza) were then added to each section employed in the test. The test chemical was mixed in such proportions with a 2% aqueous solution of cyclohexanone and surfactant (3:1 ratio) as to provide for a p.p.m. concentration of the test chemical in the Petri plate sections when 0.5 m1. of the mixture was added to the nutrient solution. As a control, the corresponding dilution of solvent and surfactant alone were added to one plate section. The Petri plates were then placed under a 3-tube, 40-watt fluorescent light about 4" above the tops of the plates.

After 48 hours the number of fronds were counted and an injury factor was assigned as appropriate. From the foregoing a corrected percentile control (or inhibition) was calculated.

The results were as follows:

Percent Compound control (a)- l-(l-oyclohexen-l-yl)-3-(3,4-dichlorophenyl)-l-methyl- 40 urea.

(0)-..- 1-(Z-methyl-I-cyclohexen-l-yl)-1-methyl-3-(3,4-dichloro- 59 phenyDurea.

It has been found that the compounds of this invention (i.e. having the double bond in the 1-position of the cycloalkenyl group) are unpredictably and unobviously superior to their position isomers (i.e. compounds which are otherwise identical except for having the double bond in the 2-position of the cycloalkenyl group). Data in support of that conclusion will be found below.

EXAMPLES 103-105 TABLE IV 5 lbs/acre Better rating Example The 2-one Example Z-ene 103 isomer 103 isomer Morning glory 1 0 X Wild oat".-. 1 0 X Brome 1 0 X Rye grass 0 0 Radish. 1 1 Sugar beet 2 1 X FoxtaiL. 1 2 X Crab grass 3 2 X Pigweed... 3 2 X Soybe n 0 Wild buckwheat 3 2 X Tomato 2 1 X Sorghum 0 1 X Total 18 12 1 Example 103 is 3-pheny1-1-methyI-1-(l-eyclohexen-l-yl) urea. 1 The 2-ene isomer is 3-phenyl-l-methyl-1-(Z-eyclohexen-l-yl) urea.

The data in Table IV clearly shows the compound of this invention to be superior to its respective isomer.

TAB LE V 5 lbs/acre Better rating Example The 2-ene 4 isomer Radish wowwrovco NNMNNNNNN 1 Example 104 is 3-(3,4-diohlorophenyl)-1-methyl-l-(l-cyclohexen-l-yl) ea I; The Z-eneisomer is 8-(3,4-dichlorophenyl)-1-methyl-1-(Z-eyclohexen-ly urea.

The data in Table V clearly shows the compound of this invention to be superior to its respective isomer.

TAB LE VI 1 Ib./acre Better rating Example The 2-ene Example 2ene 10 isomer 2 105 isomer Morning glory 2 0 X Wheat 2 0 X 2 0 X 2 0 X Hemp sesbania 3 0 X Lambsquarters 3 2 X Sugar beet 3 1 X Smartweed- 3 0 X Velvet leaf 3 1 X Crab grass 3 1 X Downy brome 2 0 X Panieum Spp 3 0 X Soybean 3 0 X Barnyard grass 3 1 X Wild buckwheat 3 1 X 2 0 X 1 Example 105 is 3-(o-fiuorophenyl)-l-methyl-1-(1-oyelo-hexen-1-yl) urea.

2 The 2-ene isomer is 3 (o-fluorophenyl)-1methyl-1-(2-cyclohexen-1-y1) urea.

The data in Table VI clearly shows the compound of this invention to be superior to its respective isomer.

EXAMPLES l06-107 Following the general post-emergent application procedure set forth in Example 100, the comparative experiments reported below were carried out using a concentration of 0.2% (i.e., about 4 lb./ acre dosage rate). The results in these experiments are set forth in T ables VII and VIII.

TABLE VII Better rating Example The 2-ene Example 2ene 106 1 isomer 1 106 isomer 4 1 1 o o a 2 i i 2 1 X 10 4 4 4 2 x 4 3 x 4 4 1 o X Total s2 25 15 1 Example 106 is 3-(o-fluorophenyl)-1-methyl-1-(l-eyelohexen-l-yl) urea.

2 The Z-ene isomer is 3-(o-fluorophenyl)-1-methyl-1-(l-eyelohexen-l-yl) urea.

The data in Table VII clearly shows the compound of this invention to be superior to its respective isomer.

1 Example 107 is 3-phenyl-1-methyl 1-(leyolohexen-1-yl) urea.

9 The 2-ene isomer is 3-phenyl-1-methyl-1-(1-cyc1ohexen-1-yl) urea.

The data in Table VIII clearly shows the compound of this invention to be superior to its respective isomer.

As mentioned hereinbefore the phytotoxic compositions of this invention comprise an active ingredient and one or more phytotoxic adjuvants. As used herein, the term adjuvant means to help or assist in the preparation of the formulation, application thereof or in enhancing the herbicidal activity or adding of different biological activity as is all well known in the art. The adjuvant can be solid or liquid extenders, carriers, diluents, conditioning agents and the like. Preferred phytotoxic compositions containing the active ingredients of this invention have been developed so that the active ingredients can be used to the greatest advantage to modify the growth of plant systems in soil. The preferred compositions comprise certain wettable powders, aqueous suspensions, dust formulations, granules, emulsifiable oils and solutions in solvents. In general these preferred compositions can all contain one or more surface-active agents.

Surface-active agents which can be used in the phytotoxic compositions of this invention are set out, for example, in Searle US. Patent 2,426,417, Todd US. Patent 2,655,447, Jones US. Patent 2,412,510 and Lenher US. Patent 2,139,276. A detailed list of such agents is also set forth by J. W. McCutcheon in Soap and Chemical Specialties, November 1947, page 811 et seq., entitled, Synthetic Detergents; Detergents and EmulsifiersUp to Date (1960), by I. W. McCutcheon, Inc., and Bulletin E-607 of the Bureau of Entomology and Plant Quarantine of the U.S.D.A. In general, less than 15 parts by weight of the surface-active agent is present per 100 parts by weight of the phytotoxic composition. 70

Wettable powders are water-dispersible compositions containing one or more active ingredients, an inert solid extender and one or more wetting and dispersing agents. The inert solid extenders are usually of mineral origin such as the natural clays, diatomaceous earth and synthetic minerals derived from silica and silicate. Examples of such extenders include kaolinites, attapulgite clay and synthetic magnesium silicate.

Preferred wetting agents are alkyl benzene and alkyl naphthalene sulfonates, sulfated fatty alcohols, amines or acid amides, long chain acid esters of sodium isothionate, esters of sodium sulfosuccinate, sulfated or sulfonated fatty acid esters, petroleum sulfonates, sulfonated vegetable oils and ditertiary acetylenic glycols. Preferred dispersants are methyl cellulose, polyvinyl alcohol, sodium lignin sulfonates, polymeric alkyl naphthalene sulfonates, sodium naphthalene sulfonate, polymethylene bisnaphthalenesulfonate and sodium N-methyl-N-(long chain acid) taurates.

The wettable powders compositions of this invention usually contain from about 5 to 95 parts of active ingredient, from about 0.25 to about 3.0 parts of wetting agent, from about 0.25 to about 7 parts of dispersant and from about 4.5 to about 94.5 parts of inert solid extender, all parts being by weight of the total composition. Where required from about 0.1 to 2.0 parts by weight of the solid inert extender can be replaced by a corrosion inhibitor or anti-foaming agent or both.

Aqueous suspensions are usually prepared by mixing together an aqueous slurry of water-insoluble active ingredient in the presence of dispersing agents to obtain a concentrated slurry of very finely-divided particles. The resulting concentrated aqueous suspension is characterized by its extremely small particle size, so that when diluted and sprayed coverage is very uniform.

Dusts are dense finely-divided particulate compositions which are intended for application to the soil in dry form. Dusts are characterized by their free-flowing and rapid settling properties so that they are not readily wind-borne to areas where they are of no value. Dusts contain primarily an active ingredient and a dense, free-flowing, finelydivided particulate extender. However, their performance is sometimes aided by the inclusion of a wetting agent such as those listed hereinbefore under wettable powder compositions and convenience in manufacture frequently demands the inclusion of an inert, absorptive grinding aid. Suitable classes of grinding aids are natural clays, diatomaceous earth and synthetic minerals derived from silica or silicate. Preferred grinding aids include attapulgite clay, diatomaceous silica, synthetic fine silica and synthetic calcium and magnesium silicates.

The inert finely-divided solid extender for the dusts can be of vegetable or mineral origin. The solid extenders are characterized by possessing relatively low surface areas and are poor in liquid absorption. Suitable inert solid extenders for phytotoxic dusts include micaceous talcs, pyrophyllite, dense kaolin clays, ground calcium phosphate rock and tobacco dust. The dusts usually contain from about 0.5 to 99 parts active ingredient, 0 to 50 parts grinding aid, 0 to 3 parts wetting agent and 1 to 99.5 parts dense solid extender, all parts being by weight based on the total weight of the dust.

The wettable powders described above may also be used in the preparation of dusts. While such wettable powders could be used directly in dust form, it is more advantageous to dilute them by blending with the dense dust diluent. In this manner, dispersing agents, corrosion inhibitors, and anti-foam agents may also be found as components of a dust.

Emulsifiable oils are usually solutions of active ingredient in water-immiscible solvents together with a surfactant. Suitable solvents for the active ingredient of this invention include hydrocarbons and water-immiscible ethers, esters or ketones. Suitable surfactants are anionic, cationic and non-ionic such as alkyl aryl polyethoxy aloohols, alkyl and alkyl aryl polyether alcohols, polyethylene sorbitol or sorbitan fatty acid esters, polyethylene glycol fatty esters, fatty alkylol amide condensate, amine salts of fatty alcohol sulfates together with long chain alcohols and oil soluble petroleum sulfonates or mixtures thereof. The emulsifiable oil compositions generally contain from about to 95 parts active ingredient, about 1 to parts surfactant and about 4 to 94 parts solvent, all parts being by weight based on the total weight of emulsifiable oil.

Granules are physically stable particulate compositions comprising active ingredient adhering to or distributed through a basic matrix of an inert, finely-divided particulate extender. In order to aid leaching of the active ingredient from the particulate, a surfactant such as those listed hereinbefore under wettable powders can be present in the composition. Natural clays, pyrophyllites and vermiculite are examples of operable classes of particulate mineral extenders. The preferred extenders are the porous, absorptive, preformed particles such as preformed and screened particulate attapulgite or heat expended, particulate vermiculite, and the finely-divided clays such as kaolin clays, hydrated attapulgite or bentonitic clays. These extenders are sprayed or blended with the active ingredient to form the phytotoxic granules.

The mineral particulates which are used in the granular phytotoxic compositions of this invention usually have a size range of 10 to 100 mesh, but preferably such that a large majority of the particles have from 14 to 60 mesh with the optimum size being from 20 to 40 mesh. Clay having substantially all particles between 14 and 80 mesh and at least about 80 percent between 20 and 40 mesh is particularly preferred for use in the present granular compositions. The term mes as used herein means U.S. Sieve Series.

The granular phytotoxic compositions of this invention generally contain from about 1 part to about 30 parts by Weight of N-(l-cycloalken-l-yl) urea per 100 parts by weight of clay and 0 to about 4 parts by weight of wetting agent per 100 parts by weight of clay. The preferred phytotoxic granular compositions contain from about 5 parts to about 25 parts by Weight of active ingredient per 100 parts by weight of clay.

The phytotoxic compositions of this invention can also contain other additaments, for example, fertilizers, other phytotoxicants, pesticides and the like, used as adjuvant or in combination with any of the above-identified adjuvants.

The compounds of this invention may be used in combination with known herbicides in order to provide enhanced biological effectiveness. The use of various herbicides in combination at the time of a single application or sequentially is common in practice. Herbicides which may be used in combination with the compounds of this in vention include but are not limited to: substituted phenoxyaliphatic acids such as 2,4-dichlorophenoxyacetic acid; 2,4,S-trichlorophenoxyacetic acid, 2-methyl-4-chlorophenoxyacetic acid and the salts, esters and amides thereof; triazine derivatives, such as 2-chloro-4-ethylamino-6-isopropylamino-s-triazine; 2,4 bis(isopropylamino)-6-methoxy-s-triazine and 2-methylmercapto-'4, 6-bis(isopropylamino)-s-triazine; urea derivatives such as 3-(3,4-dichlorophenyl)-l,1-dimethylurea and 3-(m-trifluoromethylphenyl)-1,1-dirnethylurea and 3 (3,4-dichlorophenyl)-l-methoxy-l-methylurea; pyridylium derivatives such as 1,1- ethylene-2,2-dipyridylium dihalide; acetanilides such as N-isopropyl-alpha-chloroacetanilide, and 2-chloro-2',6'-diethyl-N-methoxymethyl acetanilide; acetamides such as N,N-diallyl-alpha-chloroacetamide, carbamates such as ethyl-N,N-di-n-propylthiolcarbamate, and 2,3 dichloroallyl diisopropylthiolcarbamate; substituted uracils such as S-bromo 3-sec-butyl-6-methyluracil, substituted anilines such as N,N dipropyl-alpha,alpha,alpha-trifluoro-2,6-dinitro-p-toluidine; pyridazone derivatives such as S-amino- 4-chloro-2-phenyl-3-(2H)-pyridazinone, and the like.

Fertilizers useful in combination with the active ingredients include, for example ammonium nitrate, urea and superphosphate. Other useful additaments include materials in which plant organisms take root and grow such as compost, manure, humus, sand and the like.

When operating in accordance with the present invention, effective amounts of the N-(1-cycloalken-1-yl)ureas are dispersed on or in the soil or plant growth media and applied to plant systems in any convenient fashion. Application to the soil or growth media can be carried out by simply mixing with the media, by applying to the surface of the soil and thereafter dragging or discing into the soil to the desired depth, or by employing a liquid carrier to accomplish the penetration and impregnation. The application of liquid and particulate solid phytotoxic compositions to the surface of soil or to plant systems can be carrier out by conventional methods, e.g., power dusters, boom and hand sprayers and spray dusters. The compositions can also be applied from airplanes as a dust or a spray because of their effectiveness at low dosages. In a further method, the distribution of the active ingredients in soil can be carried out by admixture with the water employed to irrigate the soil. In such procedures, the amount of water can be varied with the porosity and water holding capacity of the soil to obtain the desired depth of distribution of the phytotoxicants.

The application of an effective or phytotoxic amount of the N-(l-cycloalken-l-yl)ureas to the soil or growth media or plant systems is essential and critical for the practice of one embodiment of the present invention. The exact amount of active ingredient to be employed is dependent upon the response desired in the plant as well as such other factors as the plant species and stage of development thereof, the specific soil and depth at which the active ingredients are distributed in the soil and the amount of rainfall as Well as the specific N-( l-cycloalken- 1-yl)urea employed. In foliar treatment for the control or modification of vegetative growth, the active ingredients are applied in amounts from about 1 to about 50 or more pounds per acre. In applications to soil for the control or modification of the growth of germinant seeds, emerging seedlings and established vegetation, the active ingredients are applied in amounts from about 1 to about 50 or more pounds per acre. It is believed that one skilled in the art can readily determine from this specification, including examples, the application rate for any specific situation.

The terms soil and growth media are employed in the present specification and claims in their broadest sense to be inclusive of all conventional soils as defined in Websters New International Dictionary, second edition, unabridged (1961). Thus, the terms refer to any substance or media in which vegetation may take root and grow, and are intended to include not only earth but compost, manure, muck, humus, sand and the like, adapted to support plant growth.

While the illustrative embodiments of the invention have been described hereinbefore with particularity, it Will be understood that various other modifications will be apparent to and can readily be made by those skilled in the art without departing from the scope and spirit of the invention. Accordingly, it is not intended that the scope of the present invention be limited to the examples and description set forth herein but rather be construed as encompassing all the features which would be treated as equivalents by those skilled in the art to which the invention pertains.

What is claimed is:

1. A phytotoxic composition comprising an inert aduvant and an effective amount of N-(l-cyclohexen-l-yl) urea of the formula wherein R is selected from the group consisting of alkyl having from 1 to 12 carbon atoms and alkoxyalkyl having from 2 to 8 carbon atoms, each R is independently selected from the group consisting of alkyl having from 1 to 4 carbon atoms and halogen, each R is independently selected from the group consisting of cyano and nitro, b is one of the integers from to 3, inclusive, 0 is one of the integers from 0 to 2, inclusive, provided that the total of b and c is a maximum of three, and X is selected from the group consisting of oxygen and sulfur.

2. A phytotoxic composition of claim 1 in which X is oxygen.

3. A phytotoxic composition of claim 2 in which R is alkyl.

4. A phytotoxic composition of claim 3 in which R is halogen, c is zero.

5. A phytotoxic composition of claim 4 in which R is methyl, R is fluorine, b is one and the fluorine is in the 2-position.

6. A phytotoxic composition of claim 4 in which R is chlorine and b is twO.

7. A method which comprises applying to plant systems a phytotoxic effective amount of an N-( l-cycloalken-l-yl) urea of the formula R X H R wherein R is selected from the group consisting of alkyl having from 1 to 12 carbon atoms and alkoxyalkyl having from 2 to 8 carbon atoms, each R is independentlyselected from the group consisting of alkyl having from 1 to 4 carbon atoms and halogen, each R is independently selected from the group consisting of cyano and nitro, b is one of the integers from 0 to 3, inclusive, 0 is one of the integers from 0 to 2, inclusive, provided that the total of b and c is a maximum of three, and X is selected from the group consisting of oxygen and sulfur.

8. A method of claim 7 in which X is oxygen.

9. A method of claim 8 in which R is alkyl.

10. A method of claim 9, in which R is halogen, c is zero.

11. A method of claim 10 in which R is fluorine, b is one and the fluorine is in the 2-position.

12. A method of claim 11 in which the active ingredient is 1-(l-cyclohexen-l-yl)-1-methyl-3-(o-fiuorophenyl)urea.

13. A method of claim 10 in which the active ingredient is 1-(l-cyclohexen-l-yl)-1-methyl-3-(3,4-dichlorophenyl)urea.

14. A method of claim 10 in which the active ingredient is 1-(l-cyclohexen-l-yl)-l-methyl-3-(p-bromophenyl)urea.

15. A method of claim 10 in which the active ingredient is 1 (1 cyclohexen 1 yl) 1 methyl 3 (3- trifluoromethylphenyl) urea.

References Cited UNITED STATES PATENTS 3,385,693 5/1968 Luckenbaugh 71-120 3,558,303 1/1971 Gobeil 71-120 2,661,272 12/1953 Searle 71-119 3,320,311 5/1967 Rai 260552 3,075,835 1/1963 Fischer 71-99 3,352,662 11/1967 Klopping et a1. 71-118 3,326,942 6/1967 Geary 71-118 3,385,690 5/1968 Luckenbaugh 71-119 3,424,571 1/1969 Bondouy et al. 71-92 LEWIS GOTTS, Primary Examiner G. HOLLRAH, Assistant Examiner US. Cl. X.R.

260-465 D, 552 R, 553 A, 558 S; 71-66, 70, 72, 76, 99, 105, 106 

